CN1084643C - Catalysts for preparing chlorine from mydrogen chloride - Google Patents
Catalysts for preparing chlorine from mydrogen chloride Download PDFInfo
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- CN1084643C CN1084643C CN95118842A CN95118842A CN1084643C CN 1084643 C CN1084643 C CN 1084643C CN 95118842 A CN95118842 A CN 95118842A CN 95118842 A CN95118842 A CN 95118842A CN 1084643 C CN1084643 C CN 1084643C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/20—Improvements relating to chlorine production
Abstract
A method for preparing an improved catalyst for use in the preparation of chlorine by the oxidization of hydrogen chloride with an oxygen-containing gas. The catalyst mainly comprises chromium oxide and can be used for a long period of time particularly under low oxygen content conditions, and the activity of the catalyst does not easily deteriorate, and in other words, the catalyst has a long life. Furthermore, there are disclosed the catalyst obtained by this preparation method, and a method for preparing chlorine from hydrogen chloride by the use of the catalyst. The method for preparing the improved catalyst comprises adding copper, an alkali metal and a rare earth metal, or adding chromium, copper, an alkali metal and a rare earth metal to a catalyst containing chromium oxide as a main component, and then calcining the catalyst at a temperature of 800 DEG C. or less.
Description
The present invention relates to prepare the improved catalyzer that chlorine is used, prepare the method for this improvement catalyzer and use this improved catalyzer to prepare the method for chlorine from hydrogenchloride by the catalyzed oxidation of hydrogenchloride.
Chlorine has been produced in electrolysis by sodium-chlor on a large scale, but is difficult to regulate chlorine and the balance between supply and demand between the caustic alkali that chlorine generates.On the other hand, by the chlorination reaction of organic compound, or when reacting, produce a large amount of hydrogenchloride by way of parenthesis with carbonyl chloride, and it is much bigger to produce muriatic its demand of amount comparison by way of parenthesis, therefore will spend a large amount of processing costss for a large amount of hydrogenchloride of handling discharging.
If can make chlorine from hydrogenchloride, so not only can satisfy demand, nor can cause the unevenness between supply and demand between chlorine and the caustic alkali amount of chlorine with high-level efficiency.
Advise using chromated oxide as the oxidation of hydrogen chloride catalyzer, but also do not reported the result that this catalyzer can be brought into play is enough to stand the industrial performance of using.
For example, a kind of method of suggestion is included under about 400 ℃, hydrogenchloride flow through use anhydrous chromic acid or chromium nitrate aqueous solution dipping appropriate carrier, carry out thermolysis and the catalyzer that makes then, behind catalyst deactivation, stop to add hydrogenchloride, this activity of such catalysts is recovered the air introducing, after this stop to add air, add hydrogenchloride (No. 584790, English Patent) again.
And, also have disclosed other technology, wherein be to utilize chromated oxide to be loaded in the catalyzer for preparing on the carrier, under 420 ℃-430 ℃ temperature of reaction, at 380hr with dichromate or blackish green
-1Air speed makes hydrogenchloride and wherein contained oxygen reaction, and the transformation efficiency of hydrogenchloride is by on average counting 67.4% (No. 676,667, English Patent).In air speed is 680hr
-1In this case, transformation efficiency is 63%.In the time of 340 ℃, observe reaction, but under this temperature, transformation efficiency is at 65hr
-1Air speed under, low to 52%.Therefore, because the high reaction temperature of these methods and low air speed are not suitable for industrial implementation.
On the other hand, have been found that, at 800 ℃ or be lower than under the temperature of this temperature, the chromium oxide catalyst that a kind of compound that generates by calcining chromic acid aqueous solution and ammonia react makes has been brought into play high activity (Japan's special permission publication number 275104/1986) in hydrogen chloride oxidation reaction, utilize this catalyzer, can be than traditional known catalysts low temperature and the air speed of Geng Gao prepare chlorine.
But, above-mentioned catalyzer also has problem, when using in the oxidizing reaction at hydrogen chloride gas, behind reaction beginning some months, activity of such catalysts just degenerates, the other problem of above-mentioned catalyzer is that doubly (overrate=150-200%) is so that keep high transformation efficiency for needed oxygen amount reaches theoretical amount in the oxidizing reaction 2.5-3.A kind of technology of the catalyzer that degenerates as activating activities, a kind of method of having proposed are included in and make catalyzer contact (Japan's special permission publication number 254846/1987) with hydrogen chloride gas and/or oxygen-containing gas in the high temperature gas phase.But, if the activatory catalyzer uses in the oxidizing reaction of hydrogen chloride gas in this way,
This catalyzer activity that can keep equaling live catalyst begins time by several days from reaction so, but after a week or longer time, activity of such catalysts begins to degenerate, and the activatory catalyzer just can not be convenient to use for a long time as a result.
Have, the another kind of activation method that has proposed comprises the solution impregnating catalyst with chromic salts or chromated oxide again, then at 800 ℃ or be lower than the temperature lower calcination (Japan special permission publication number 221145/1991) of this temperature.Yet, when the activatory catalyzer is used for the oxidizing reaction of hydrogen chloride gas in this way, the activity that this catalyzer also can keep equaling live catalyst begins to reach several days time from reaction, and after one month or longer time, activity of such catalysts just begins to degenerate.Therefore, the activatory catalyzer also has a problem that can not stand life-time service in this way.
The method for preparing chlorine with copper bearing catalyst oxidation hydrogenchloride is former with regard to known Deacon reaction, and, also proposed to comprise the catalyzer of the numerous species of cupric chloride, Repone K and a kind of the 3rd component that is selected from various compound afterwards about the copper containing catalyst by Deacon invention in 1868.But any industry in these catalyzer is used, for obtaining enough speed of reaction, just must improve temperature of reaction, but improve the volatilization that temperature of reaction can cause catalyst component, its as a result activity of such catalysts in the time durations of a weak point, just degenerate.In brief, this catalyzer is having a fatal problem aspect life of catalyst.In addition, also known raising temperature of reaction can cause the accumulation of catalyzer, particularly when catalyzer is used as fluid catalyst, the serious problems that suppress rheomorphism is arranged, and therefore this catalyzer does not just more act on.
The present invention attempts to solve above-mentioned traditional known catalysts in some problems that prepare by chloration hydro-oxidation in the chlorine, the purpose of this invention is to provide a kind of chromium-containing oxide as main ingredient, and under the low oxygen concentration condition, can use a long time durations and fully get rid of the improved catalyzer that its activity degenerates.
Another object of the present invention provides a kind of method for preparing above-mentioned catalyzer.
Another purpose more of the present invention provides a kind of method of using above-mentioned catalyzer to prepare chlorine from hydrogenchloride.
For realizing these purposes of the present invention, the inventor deeply fine studied chloration hydro-oxidation prepare the chromium-containing oxide that uses in the chlorine raising active and long-life Preparation of catalysts method.
Found that, can be by adding the catalyzer that a chromium-containing oxide prepares as the catalystic material of main ingredient with copper, a kind of basic metal and a kind of rare earth metal or with chromium, copper, a kind of basic metal and a kind of alkene earth metals, be suitable for oxygen-containing gas oxidation chlorination hydrogen and prepare chlorine, and this catalyzer is compared as the catalyzer of main ingredient with traditional known chromium-containing oxide, higher activity is arranged, and its activity does not degenerate in time, in other words, this catalyst life is long, and its activity can keep under the situation of low oxygen concentration effectively.In addition, find that also this catalyzer during reaction can not cause the volatilization of catalyst component and the accumulation of catalyzer, and traditional copper to be the Deacon catalyzer of major constituent have these problems. therefore, this catalyzer holds out against secular industry and uses.When the preparation catalyzer, for example can adopt the salts solution of respective metal.
And, also found the process for reactivation of chromium oxide catalyst, comprise copper, a kind of basic metal and a kind of rare earth metal, or with chromium, copper, a kind of basic metal and a kind of rare earth metal add a traditional chromium-containing oxide as main ingredient the reaction for preparing chlorine from hydrogenchloride in the already used active catalyzer that degenerates.According to this process for reactivation, the active chromium oxide catalyst that degenerates can activate, be reactivate, and so the catalyzer of reactivate holds out against secular industry use, and do not cause above-mentioned those problems that traditional chromium oxide catalyst process for reactivation has.Therefore, the present invention has finished on the basis of above-mentioned these knowledge.
In other words, the present invention is by following forming.
(1) a kind of improvement catalyzer for preparing chlorine by oxidation chlorination hydrogen, it is by with copper, a kind of basic metal and a kind of rare earth metal, or chromium, copper, a kind of basic metal and a kind of rare earth metal added makes in the traditional catalyzer of chromium-containing oxide as main ingredient.
(2) by the catalyzer of (1), wherein chromium-containing oxide is at 800 ℃ or is lower than under this temperature as the catalyzer of main ingredient, and calcining contains the catalyzer that the mixture of reaction product that a kind of silicon compound and chromic salts and ammonia or one can disengage the compound of ammonia prepares.
(3) by the catalyzer of (1), wherein chromium-containing oxide is one to have prepared the active spent catalyst of degenerating of chlorine as oxidation chlorination hydrogen as the catalyzer of main ingredient.
(4) by the catalyzer of (1), wherein basic metal is potassium.
(5) by the catalyzer of (1), wherein rare earth metal is a lanthanum.
(6) by the catalyzer of (1), wherein copper, potassium, lanthanum are that the atomic ratio of the chromium in the catalyzer of main ingredient is respectively 0.01-0.3,0.005-0.2 and 0.01-0.3 to chromium-containing oxide.
(7) by the catalyzer of (2), wherein after calcining, silicon compound is with SiO
2Form exists, chromated oxide and SiO
2Content than for 5/95-95/5.
(8) a kind of Preparation of catalysts method for preparing chlorine with oxygen-containing gas oxidation chlorination hydrogen from hydrogenchloride, this method comprises the solution with cupric, a kind of basic metal and a kind of rare earth metal, or a kind of chromium-containing oxide of solution impregnation that contains chromium, copper, a kind of basic metal and a kind of rare earth metal be main ingredient catalyzer step and at 800 ℃ or be lower than the step of the impregnated catalyzer of temperature lower calcination of this temperature.
(9) by the method for preparing catalyzer of (8), wherein restraining chromium-containing oxide with the solution impregnation one of 0.2-2ml is that the such ratio of catalyzer of main ingredient is flooded the catalyzer that chromium-containing oxide is a main ingredient.
(10) a kind of method for preparing chlorine with oxygen-containing gas oxidation chlorination hydrogen, this method comprises utilizing to be passed through copper, a kind of basic metal and a kind of rare earth metal, or with chromium, copper, a kind of basic metal and a kind of rare earth metal add the step that a chromium-containing oxide is the catalyzer that makes in the catalyzer of main ingredient.
(11) by the method for preparing chlorine of (10), wherein hydrogenchloride be with oxygen-containing gas in the oxygen reaction, to the hydrogenchloride of 1ml, the mol ratio of oxygen is 1/4-1.
The catalyzer that can be main ingredient as the chromium-containing oxide of base catalyst of the present invention can be above-mentioned various forms, and can prepare by above-mentioned method, but for example, can be by at 800 ℃ or be lower than under the temperature of this temperature, calcining contains the mixture that silicon compound and chromic salts such as chromium nitrate, chromium chloride or organic acid chromic salts and ammonia maybe can disengage the reaction product of the compound of ammonia such as urea and prepares this catalyzer.Ratio of mixture for chromium and silicon has no particular limits, but Cr
2O
3With SiO
2The weight ratio of (form in the last incinerating catalyzer), i.e. Cr
2O
3/ SiO
2The 5/95-95/5 scope of being everlasting.
In the present invention, as chromium, copper, basic metal and rare earth metal composition are added chromium-containing oxide is the technology of a kind of catalyzer of main ingredient, can adopt a kind of preparation method of traditional known catalysts, for example dipping method, coprecipitation method or CVD (Chemical Vapor Deposition) method.These above-mentioned methods, pickling process is more effective, and its operation is also simple.
An example of dipping method is the solution with a kind of cupric, basic metal and rare earth metal, or with a kind of above-mentioned chromated oxide of solution impregnation that contains chromium, copper, a kind of basic metal and a kind of rare earth metal, then at 800 ℃ or be lower than the temperature lower calcination of this temperature.
In the method for the invention, it is necessary using copper, basic metal and rare earth metal three components, if this three component lacks any, activity of such catalysts just can not obviously improve so, and result's above-mentioned purpose of the present invention just more can not realize.
The representative example of the chromium component that can use in the present invention comprises water-soluble chromic salts, for example chromium nitrate and chromium chloride, and water miscible chromated oxide, for example anhydrous chromic acid.The concentration of chromic salts or chromated oxide is preferably in the 5-45% scope.Last burnt catalyst form Cr
2O
3With SiO
2Weight ratio, i.e. Cr
2O
3/ SiO
2Preferably in the scope of 5/95-95/5.
The representative instance of the copper component that can use in the present invention comprises cupric nitrate, copper sulfate, cupric chloride and copper oxide, and the example of operable basic metal and rare earth metal comprises nitrate, vitriol, muriate and the oxide compound of these metals.The representative example of alkaline components comprises KNO
3, K
2SO
4, KCl, NaNO
3, Na
2SO
4, NaCl and Na
2O, the representative example of rare earth metal salt comprises nitrate, vitriol, halogenide and the oxide compound of La, Ce, Pr, Nd, Pm, Sm and Eu, and above-mentioned in all these, the salt of preferred La.When the concentration of copper, basic metal and rare earth metal is high, can obtain their bigger influences, but copper, potassium and lanthanum are the atomic ratio of the chromium in the catalyzer of main ingredient to chromium-containing oxide, respectively preferably at 0.01-0.3,0.005-0.2 and 0.01-0.3.
Under according to the present invention, situation with the solution impregnating carrier of copper, basic metal and rare earth metal, dipping method is not particularly limited, can use any above-mentioned pre-soaked method, the dipping that wherein contains the chromium component solution is to carry out before the dipping of cupric, basic metal and rare earth metal solution, the while dipping method, wherein the dipping of chromium component is that dipping with other component carries out simultaneously, back dipping method, and wherein the dipping of chromium component is to carry out behind other component dipping.In all above-mentioned methods, in most of the cases, preferably according to pre-soaked method, other component dipping that is immersed in of chromium component carries out before.
With in the solution impregnating carrier, this solution has dissolved said components, and the temperature of solution is preferably at 25-70 ℃, more preferably 25-35 ℃.The amount of solution is to realizing that evenly dipping is an important factor, and its amount is that preferred specific surface area by catalyzer changes.Usually, the specific surface area at catalyzer is 270-320m
2Under the situation of/g, it is doubly so much that the amount of solution is preferably the 1/2-2 of catalytic amount.Specific surface area at catalyzer is 200-270m
2Under the situation of/g, the amount of solution is preferably the 1/3-1/2 of catalytic amount; And be 200m in the specific surface area of catalyzer
2Under/g or the situation less than this value, the amount of solution be preferably catalytic amount 1/3 or less than this value.These requirements are that optimum is used for even dipping.
If desired, can divide and carry out dip treating several times, and can not cause any problem of performance, but in this case, require repeated impregnations and pre-calcination (150-300 ℃) for several times.But, preferred vector is in the solution impregnation of once using predetermined amount.Behind the dipping, carried out married operation about one hour by vibrating a container that catalyzer and the aqueous solution or organic solvent solution are housed, the used component of catalyzer all can be mixed like this, but under the low situation of the wet situation of catalyzer, this vibration/mixing time requires to prolong several times.After this, the catalyzer that carries out combination treatment is at 800 ℃ or be lower than the temperature lower calcination of this temperature.Be immersed in metal component evaporable viewpoint on the carrier from prevention, calcining temperature is preferably at 300-650 ℃, more preferably 350-550 ℃.
In the presence of catalyzer of the present invention, owing to, can use the chlorination of chemical industry field organic compound with the raw material of hydrogenchloride as preparation chlorine, or react the hydrogenchloride that obtains as by product with carbonyl chloride, this is economical.But this supply of hydrogenchloride is limited.
The oxidation of hydrogen chloride agent can use oxygen-containing gas, and oxygen or air usually uses.About the type of reactor, fixed bed and fluidized-bed reactor all are practical, but all use fluidized-bed reactor usually, because hydrogen chloride oxidation reaction will produce a large amount of heat, and fluidized-bed reactor is easy to get rid of heat.Under the fluid bed-type of reactor situation, often use oxygen, and under the fixed-bed type reactor situation, often use air.
The mol ratio of oxygen is 1/4mol oxygen (equivalent) usually to one mole of hydrogenchloride in hydrogenchloride and the operable oxygen-containing gas.In general, employed oxygen often surpasses normal 5-200%.These unstripped gass can be with being the inert nitrogen dilution to main reaction.
Under the fluid bed-type of reactor situation, hydrogenchloride suits with the feed rate adding catalyst bed of 200-1800NL/hr/kg-catalyzer.
Temperature of reaction Chang Youxuan is at 300-450 ℃, more preferably at 360-420 °.
Main reaction all is practical at normal atmosphere with adding under any one situation of depressing, but in general, Chang Youxuan is at 2-11kg/cm
2The adding to depress of (definitely), carry out.
When a traditional chromium-containing oxide be main ingredient known catalysts use under the above-mentioned reaction conditions reach several months to half a year during after, activity of such catalysts degenerates, and is reduced to 50-60% from the 70-80% transformation efficiency of initial hydrogenchloride.
In the present invention, as with the base catalyst of chromium-containing oxide as main ingredient, the known spent catalyst that can utilize traditional activity that mainly comprises chromated oxide to degenerate.According to the present invention, this spent catalyst can be used the solution of cupric, a kind of basic metal and a kind of rare earth metal, or a kind of solution impregnation that contains chromium, copper, a kind of basic metal and a kind of rare earth metal, to recover this activity of such catalysts.
According to the present invention, a kind of improved catalyzer of using in the reaction for preparing chlorine by oxidation of hydrogen chloride is provided, this improved catalyzer has higher activity, and activity degenerates littler than traditional known catalysts in time.At this moment, just can make this improved catalyzer by simple method.In traditional chromium oxide catalyst, for keeping oxidizing reaction, require oxygen excessive in a large number, but the improved catalyzer of the present invention can use under oxygen concn has only the oxygen concn of 1/3-1/2 of traditional chromium oxide catalyst, even under this condition, during life-time service, improve activity of such catalysts and degenerate also very little when improved catalyzer.The of the present invention improved catalyzer that makes like this, even be under the situation of 50% low oxygen concentration in the oxygen excess rate, can keep highly active performance for a long time.And, according to the present invention, comprise that mainly chromated oxide and the active conventionally known catalyzer that degenerates after the medium-term and long-term use of hydrogen chloride oxidation reaction can activate and reactivate.So the catalyzer of reactivate has high reactivity, even when life-time service, has given play to the performance that equals live catalyst.
Below, reference example is described method of the present invention in more detail.By the way, chromium-containing oxide is to prepare by disclosed method in Japan's special permission publication number 275104/1986 as the base catalyst (hereinafter claiming " chromium oxide catalyst ") of main ingredient.
Embodiment 1
Contain 6.71gCuCl with 25ml
22H
2O, 2.85gKCl and 7.79g La (NO
3)
36H
2The aqueous solution of O dipping 50g fluidized-bed is with thin globular chromium oxide catalyst, and the median size of this catalyzer is 61 μ m, and is made up of 75% (wt) chromic oxide and 25% (wt) silicon oxide, and this catalyzer was calcined 5 hours at 510 ℃ times then.Then, with pack into the glass flows fluidized bed reactor of one inch of internal diameter of the 40g catalyzer of handling like this, respectively with 334ml/ divides and 125ml/ divides feed rate with hydrogen chloride gas and oxygen introducing fluidized-bed (oxygen excess rate=about 50%).After this, the outer wall of reaction tubes heats with electric furnace, makes the reaction tubes temperature inside can be 380 ℃, to react.
From second day of the reaction beginning, the transformation efficiency of hydrogenchloride was 78%.From the 30th day of reaction beginning, transformation efficiency 76%, even at the 60th day, transformation efficiency was 74%, and this just shows, has kept high reactivity.
Embodiment 2
According to embodiment 1 identical step, contain 12.72g Cu (NO with 55ml
3)
23H
2O, 5.19gKNO
3With 10.42g La (NO
3)
36H
2The thin globular fluidized-bed of the aqueous solution dipping 50g chromium oxide catalyst of O, the median size of this catalyzer is 50 μ m, and is made up of 75% (wt) chromic oxide and 25% silicon oxide, this catalyzer was calcined 5 hours down at 550 ℃ then.The catalyzer 40g that handled like this is according to being used in the hydrogen chloride oxidation reaction as embodiment 1 identical step.
From the 3rd day of reaction beginning, the hydrogenchloride transformation efficiency was 80%, and at the 10th day, transformation efficiency was 80%, and from the 30th day of the reaction beginning, transformation efficiency was 77%, and was 76% at the 65th day transformation efficiency, and this just shows that this activity of such catalysts is identical with embodiment 1 with the life-span.
Embodiment 3
Contain 1825.7g Cu (NO with 5.5 liters
3)
23H
2O, 548.8gKCl and 1496.3gLa (NO
3)
36H
2The chromium oxide catalyst that the thin spherical fluidized-bed of aqueous solution dipping 4kg of O is used, the median size of this catalyzer is 73 μ m, and is made up of 70% (wt) chromic oxide and 30% (wt) silicon oxide, this catalyzer was calcined 5 hours down at 550 ℃ then.Then, with pack into the nickel fluidized-bed reactor of 4 inches of internal diameters of the 4kg catalyzer of handling like this, the outer wall of reactor heats up to 400 ℃ in the sand fluidized bath.After this, introduced hydrogen chloride gas and oxygen (oxygen excess rate=about 50%) with 1400NL/ hour with 525NL/ hour feed rate respectively, to react.
From the 3rd day of the reaction beginning, the transformation efficiency of hydrogenchloride was that 81%, the 30 day transformation efficiency is 78%.From the 67th day of the reaction beginning, transformation efficiency was 77%, and this shows that activity of such catalysts degenerates minimum.
Comparative example 1-3
To chromium-containing oxide is the catalyzer of main ingredient, and it is necessary using copper, basic metal and rare earth metal three components, but when any of these components during as following omission, activity of such catalysts is very low.The results are shown in table 1.
Table 1
| Dip composition | Transformation efficiency (after three days) | |
| Comparative example 1 | There is not copper component KCl 4.72g La (NO 3) 3·3H 2O 12.48g | 15.1％ |
| Comparative example 2 | ·Cu(NO 3) 2·3H 2O 10.72g does not have alkaline components La (NO 3) 3·6H 2O 12.48g | Assemble |
| Comparative example 3 | ·Cu(NO 3) 2·3H 2O 10.72g KCl 4.72g does not have the rare earth metal component | 29.0％ |
Table 2
The reaction conditions reaction unit: internal diameter is one inch a glass flows fluidized bed reactor.The catalytic amount of reaction usefulness: the feed rate of the useless hydrogen chloride gas of 40g: 334ml/ divides the oxygen feed rate: 167ml/ branch (oxygen excess rate=about 100%) temperature of reaction: being heated to the inside reactor temperature with electric furnace is 380 ℃.Employed base catalyst in dip treating: be the identical chromium oxide catalyst that uses among the embodiment 1.
| Catalyzer is formed | Reaction result | |
| Comparative example 4 | SiO 215.0g Cu (NO 3) 23H 2O 10.72g KCl 4.72g La (NO 3) 36H 2O 6.24g | After 30 days, catalyzer is assembled, and fluidisation stops.After 3 days, transformation efficiency is reduced to 45% from 77%. |
| Comparative example 5 | SiO 215.0g Cu (NO 3) 23H 2O 5.36g KCl 2.36g La (NO 3) 36H 2O 6.24g | After 19 days, catalyzer is assembled, and fluidisation stops.After 3 days, transformation efficiency is reduced to 40% from 74% |
Comparative example 4 and 5
More traditional Deacon catalyst activity degenerates and rendezvous problem, the results are shown in table 2.The reaction conditions reaction unit: catalytic amount is used in the glass flows fluidized bed reactor reaction that internal diameter is an inch: 20g hydrogen chloride gas feed rate: 167ml/ divides the oxygen feed rate: 84ml/ branch (oxygen overrate=about 100%) temperature of reaction: being heated to the inside reactor temperature with electric furnace is 380 ℃
Employed medium in dip treating: silica gel CARiACT, Fuji chemistry of silicones product company limited makes.
Embodiment 4
With the thin globular median size of 40g be 60 μ m, the chromium oxide catalyst used of the fluidized-bed be made up of 75% (wt) chromic oxide and 25% (wt) silicon oxide internal diameter of packing into is 1 inch glass flows fluidized bed reactor.Then introduce hydrogen chloride gas and oxygen (oxygen overrate=about 100%) with the feed rate that 334ml/ divides and 167ml/ divides respectively, the reactor tube outer wall heats with electric furnace, and making the reactor tube internal temperature can be 380 ℃, to react.
From the 3rd day of the reaction beginning, the hydrogenchloride transformation efficiency was 73%.From the 30th day of the reaction beginning, transformation efficiency was 67%, the 65 day, and transformation efficiency is low to 55%.At this moment, take out used catalyzer, contain 10.72g CuCl with 50ml
22H
2O, 4.72g KCl and 12.48g La (NO
3)
23H
2O (NO
3)
36H
2The aqueous solution dipping of O, this catalyzer was calcined 5 hours down at 510 ℃ then.The catalyzer 40g that such reactivate is crossed carries out the reaction as above-mentioned same way as then.From the 3rd day of the reaction beginning, the transformation efficiency of hydrogenchloride was 77%, and at the 10th day, transformation efficiency was 72%.At 30 days of the reaction beginning, transformation efficiency was 68%, and at the 65th day, transformation efficiency was 58%, and this shows that the activity of such catalysts of reactivate and life-span are identical with live catalyst.
Embodiment 5
As in the identical step of embodiment 4, used 65 days SA spent catalyst with 40ml by with 7.2g CuCl
22H
2O and 4.27g KNO
3Add 15ml and contain 3.14gLa
2O
325% aqueous nitric acid and the solution impregnation for preparing, catalyzer is 550 ℃ of calcinings 5 hours down then.After, the catalyzer of this reactivate of 40g is by being used for hydrogen chloride oxidation reaction as embodiment 4 identical steps.
At the 3rd day of the reaction beginning, the transformation efficiency of hydrogenchloride was 74%, is 71% at the 10th day transformation efficiency, from the 30th day of the reaction beginning, transformation efficiency was 65%, at the 65th day, transformation efficiency is 57%, and this activity of such catalysts that just shows reactivate and life-span be identical with embodiment 6 approximately.
Embodiment 6
The SA spent catalyst that identical step was used 65 days in as embodiment 4 contains 9.51g Cu (NO with 40ml
3)
23H
2O, 3.87g KNO
3With 7.79g La
2(NO
3)
3H
2The solution impregnation of O, this catalyzer was calcined 5 hours down at 550 ℃ then.After, the 40g catalyzer that uses such reactivate to cross carries out hydrogen chloride oxidation reaction by identical step among the embodiment 4.At the 5th day that begins from reaction, the hydrogenchloride transformation efficiency was that 74%, the ten day transformation efficiency is 72%, at the 30th day from the reaction beginning, transformation efficiency is 64%, is 59% at the 66th day transformation efficiency, approximately identical among this activity of such catalysts that just shows reactivate and life-span and the embodiment 4.
Embodiment 7
The chromium oxide catalyst that the fluidized-bed that the microspheric median size of being made up of 70% (wt) chromic oxide and 30% (wt) silicon oxide of 4kg is 63 μ m the is used internal diameter of packing into is 4 inches a nickel fluidized-bed reactor, the reactor outer wall sand flow is moving bathe in heating reach 400 ℃.Then, introduce fluidized-bed with will give up hydrogen chloride gas and oxygen of the feed rate of 1400NL/ hour and 1000NL/ hour respectively, to react.From reaction beginning the 3rd day, the hydrogenchloride transformation efficiency was 78%, is 75% at the 30th day transformation efficiency.At the 76th day that begins from reaction, transformation efficiency was reduced to 63%.At this moment, take out used catalyst, contain 1.072kg CuCl with 5 liters then
22H
2O, 0.472kg KCl and 1.248kg La (NO
2)
36H
2The aqueous solution dipping of O, this catalyzer was calcined 5 hours down at 510 ℃.Then, the catalyzer of the such reactivate of 4kg such as above-mentioned same way as are reacted.
From the 3rd day of the reaction beginning, the hydrogenchloride transformation efficiency was 79%, is 74% at the 30th day transformation efficiency.From reaction beginning the 66th day, transformation efficiency was 63%, and this just shows that the activity of reactivating catalyst and life-span are identical with live catalyst.
Comparative example 6-8
As the catalyzer of main ingredient, it is necessary using copper, basic metal and rare earth metal three components concerning chromium-containing oxide, but during any of these components of omission described as follows, reactivation of catalyst is impossible.The results are shown in table 3.
Table 3
The reaction conditions reaction unit: internal diameter is that catalytic amount is used in 1 inch glass flows fluidized bed reactor reaction: the feed rate of 40g hydrogen chloride gas: 334ml/ divides the oxygen feed rate: 167ml/ branch (oxygen overrate=about 100%) temperature of reaction: being heated to the inside reactor temperature with electric furnace is 380 ℃.Used base catalyst in dip treating: be in embodiment 4, to begin to be reduced to 58% chromium oxide catalyst to the 65th day transformation efficiency from reaction.
| Dip composition | Transformation efficiency (after three days) | |
| Comparative example 6 | There is not copper component KCl 4.72g La (NO 3) 3·6H 2O 12.48g | 13.6％ |
| Comparative example 7 | ·Cu(NO 3) 2·2H 2O 10.72g does not have alkaline components La (NO 3) 3·6H 2O 12.48g | Assemble |
| Comparative example 8 | ·Cu(NO 3) 2·2H 2O 10.72g KCl 4.72g does not have the rare earth metal component | 27.1％ |
Embodiment 8
The 40g median size be 60 μ m, microspheroidal, the chromium oxide catalyst be made up of 75% (wt) chromic oxide and 25% (wt) silicon oxide internal diameter of packing into is one inch glass flows fluidized bed reactor.Then with the feed rate that 334ml/ divides and 167ml/ divides hydrogen chloride gas and oxygen are introduced fluidized-bed respectively, heat with electric furnace the outside of reaction tubes, makes the internal temperature of reaction tubes can be 380 ℃.The mol ratio of oxygen/hydrogen chloride gas is 1/2, and the oxygen overrate is 100%.
From the 3rd day of the reaction beginning, the transformation efficiency of hydrogenchloride was 73%.Transformation efficiency at the 30th day is 67%, and at the 65th day, transformation efficiency was reduced to 55%.
SA like this spent catalyst contains 15.3kg Cr (NO with 8.3ml
3)
39H
2The aqueous solution dipping of O was calcined 6 hours down at 520 ℃ then.After, contain 10.72gCuCl with 50ml
22H
2O, 4.72g KCl and 12.48g La (NO
3)
36H
2The aqueous solution dipping of O, the catalyzer of handling was like this calcined 5 hours down at 510 ℃.Then, the catalyzer of the such reactivate of 40g reacts by mode same as described above.
From the 3rd day of the reaction beginning, the hydrogenchloride transformation efficiency was 77%, is 72% at the 10th day transformation efficiency, from reacting the 30th day that begins, transformation efficiency is 68%, is 65% at the 65th day transformation efficiency, and this shows that the activity of reactivating catalyst and life-span are parity with or superiority over live catalyst.
Comparative example 9
The chromium oxide catalyst that the fluidized-bed that 40g is microspheric, median size is 60 μ m, be made up of 75% (wt) chromic oxide and 25% (wt) silicon oxide is used, the glass flows fluidized bed reactor of one inch of the internal diameter of packing into.Thereafter with the feed rate that 334ml/ divides and 125ml/ divides hydrogen chloride gas and oxygen are introduced fluidized-bed respectively, heat with electric furnace the outside of reaction tubes, makes the reaction tubes internal temperature can reach 380 ℃.The mol ratio of oxygen/hydrogen oxide is 3/8, and the oxygen overrate is 50%.
From the 3rd day of the reaction beginning, the hydrogenchloride transformation efficiency was 63%.At the 30th day transformation efficiency from the reaction beginning is 57%, and at the 65th day, transformation efficiency was reduced to 45%.
Embodiment 9
40g is microspheric, median size is 60 μ m, be one inch glass flows fluidized bed reactor by 75% (wt) chromic oxide and 25% (wt) silicon oxide chromium oxide catalyst that form, that fluidized-bed the is used internal diameter of packing into.Thereafter divide with 334ml/ respectively and feed rate that 125ml/ divides will give up hydrogen chloride gas and oxygen introducing fluidized-bed, the reaction tubes outer wall heats with electric furnace, makes the internal temperature of reaction tubes can be 380 ℃.The mol ratio of oxygen/hydrogenchloride is 3/8, and the oxygen overrate is 50%.
At the 3rd day that begins from reaction, the transformation efficiency of hydrogenchloride was 63%.At the 30th day transformation efficiency from the reaction beginning is 57%, and at the 65th day, transformation efficiency was reduced to 45%.At this moment, take out used catalyst, contain 15.3g Cr (NO with 8.3ml
3)
39H
2The aqueous solution dipping of O was calcined 6 hours down at 520 ℃, contained 10.72g CuCl with 50ml
22H
2O, 4.72gKCl and 12.48g La (NO
3) H
2The aqueous solution dipping of O was calcined 5 hours down at 510 ℃.Thereafter, the catalyzer of the such reactivate of 40g is by reacting as above-mentioned same way as.
At the 3rd day that begins from reaction, the transformation efficiency of hydrogenchloride was 77%, is 72% at the 10th day transformation efficiency.At the 30th day that begins from reaction, transformation efficiency was 68%, is 65% at the 65th day transformation efficiency, and this just shows that the activity of reactivating catalyst and life-span are parity with or superiority over live catalyst.
Embodiment 10
40g microspheroidal, median size be 60 μ m, be one inch glass flows fluidized bed reactor by 75% (wt) chromic oxide and 25% (wt) silicon oxide chromium oxide catalyst that form, that fluidized-bed the is used internal diameter of packing into.Thereafter this catalyzer takes out used like this catalyzer by reacting as same way as among the embodiment 7, contains 15.3g Cr (NO with 8.3ml
3)
39H
2The aqueous solution of O and 50ml contain 10.72g CuCl
22H
2O, 4.72g KCl and 12.48g La (NO
3)
36H
2The aqueous solution of O floods simultaneously, calcines 5 hours down at 510 ℃.Thereafter, the catalyzer of the such reactivate of 40g reacts in the same manner as described above.
From the 3rd day of the reaction beginning, the hydrogenchloride transformation efficiency was 77%, is 72% at the 10th day transformation efficiency, is 68% at the 30th day transformation efficiency, is 65% at the 65th day transformation efficiency, and this just shows that the activity of reactivating catalyst and life-span are parity with or superiority over live catalyst.
Embodiment 11
40g microspheroidal, median size be 60 μ m, form by 75% (wt) chromic oxide and 25% (wt) silicon oxide, fluidized-bed is with pack into the glass flows fluidized bed reactor of one inch internal diameter of chromium oxide catalyst.Thereafter, catalyzer such as embodiment 7 same way as are reacted, and take out used catalyzer, contain 20.3g Cr (NO with 8.3ml
3)
39H
2Behind the aqueous solution dipping of O, calcined 7 hours down, contain 13.72g CuCl with 50ml at 500 ℃
22H
2O, 5.72g KCl and 14.28g La (NO
3)
36H
2Behind the O aqueous solution dipping, 510 ℃ of calcinings 5 hours.Thereafter, the catalyzer of the such reactivate of 40g is to react as above-mentioned same way as.
At the 3rd day that begins from reaction, the hydrogenchloride transformation efficiency was 77%, and at the 10th day, transformation efficiency was 72%.From the 30th day of reaction beginning, transformation efficiency is 69%, and at the 65th day, transformation efficiency was 66%, and this just shows that the activity of reactivating catalyst and life-span are parity with or superiority over live catalyst.
Embodiment 12
Except that replacing the 2.85g KCl with 2.23g NaCl, by the step identical with embodiment 1, component solution with copper, a kind of basic metal and a kind of rare earth metal floods chromium oxide catalyst to prepare improved catalyzer, under the condition identical with embodiment 1, hydrogenchloride and oxygen react under the catalyzer of preparation like this.
At second day that begins from reaction, the transformation efficiency of hydrogenchloride was 75%, and at the 30th day, transformation efficiency was 72%, and at the 60th day, transformation efficiency was 70%.
Embodiment 13
Remove (NO with 7.89g Nd
3)
36H
2O replaces 7.79g La (NO
3)
36H
2Outside the O, by the step identical with embodiment 1, with the component solution of copper, a kind of basic metal and a kind of rare earth metal dipping chromium oxide catalyst preparing improved catalyzer, under the condition identical with embodiment 1, hydrogenchloride under the condition that the catalyzer that such preparation is arranged exists with oxygen reaction.
At second day of the reaction beginning, the transformation efficiency of hydrogenchloride was 77%, and at the 30th day, transformation efficiency was 75%, and at the 60th day, transformation efficiency was 74%.
Claims (10)
1. one kind by making hydrogenchloride be prepared the catalyzer of chlorine by the oxygen-containing gas oxidation, be with copper, a kind of basic metal and a kind of rare earth metal component, or chromium, copper, a kind of basic metal and a kind of rare earth metal component to add chromium-containing oxide be that the alkaline catalysts of main ingredient prepares, described alkaline catalysts is at 800 ℃ or is lower than under this temperature, and calcining comprises that a kind of silicon compound and a kind of chromic salts and ammonia can disengage maybe that the mixture of reaction product of the compound of ammonia prepares.
2. by the catalyzer of claim 1, wherein chromium-containing oxide is a conduct prepares chlorine by oxidation chlorination hydrogen the used active catalyzer that degenerates of catalyzer as the alkaline catalysts of main ingredient.
3. by the catalyzer of claim 1, wherein basic metal is potassium.
4. by the catalyzer of claim 1, wherein rare earth metal is a lanthanum.
5. by the catalyzer of claim 1, wherein with respect to chromium-containing oxide as the chromium in the alkaline catalysts of main ingredient, the atomic ratio of copper, potassium and lanthanum is respectively 0.01-0.3,0.005-0.2 and 0.01-0.3.
6. by the catalyzer of claim 1, wherein after calcining, silicon compound is with SiO
2Exist, the weight ratio of chromic oxide and silicon-dioxide is 5/95-95/5.
7. one kind by preparing the Preparation of catalysts method of chlorine from hydrogenchloride with oxygen-containing gas oxidation chlorination hydrogen, this method comprises uses cupric, the solution of a kind of basic metal and a kind of rare earth metal, or a kind of chromium that contains, copper, the solution impregnation chromium-containing oxide of a kind of basic metal and a kind of rare earth metal is the step of the alkaline catalysts of main ingredient, described alkaline catalysts is at 800 ℃ or is lower than under this temperature, calcining comprises that a kind of silicon compound and a kind of chromic salts and ammonia can disengage maybe that the mixture of reaction product of the compound of ammonia prepares, with at 800 ℃ or be lower than under this temperature, calcine the step of impregnated catalyzer.
8. the method for preparing catalyzer by claim 7, wherein chromium-containing oxide is that the catalyzer of main ingredient is that using with respect to 1 gram chromium-containing oxide is the catalyzer of main ingredient, with the dipping solution dipping of 0.2-2ml.
9. method for preparing chlorine, this method is included under the existence of catalyzer, use the step of oxygen-containing gas oxidation chlorination hydrogen, described catalyzer is by preparing with copper, a kind of basic metal and a kind of rare earth metal component or with chromium, copper, a kind of basic metal and a kind of rare earth metal component adding chromated oxide alkaline catalysts as main ingredient, described alkaline catalysts is at 800 ℃ or is lower than under this temperature, and calcining comprises that a kind of silicon compound and a kind of chromic salts and ammonia can disengage maybe that the mixture of reaction product of the compound of ammonia prepares.
10. by the method for claim 9, wherein the oxygen in hydrogenchloride and the oxygen-containing gas reacts, and with respect to 1 mole hydrogenchloride, the mol ratio of oxygen is 1/4-1.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27880494 | 1994-11-14 | ||
| JP278804/94 | 1994-11-14 | ||
| JP22309095 | 1995-08-31 | ||
| JP223090/95 | 1995-08-31 | ||
| JP228749/95 | 1995-09-06 | ||
| JP22874995 | 1995-09-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1126637A CN1126637A (en) | 1996-07-17 |
| CN1084643C true CN1084643C (en) | 2002-05-15 |
Family
ID=27330740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95118842A Expired - Lifetime CN1084643C (en) | 1994-11-14 | 1995-11-14 | Catalysts for preparing chlorine from mydrogen chloride |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5707919A (en) |
| EP (1) | EP0711599B1 (en) |
| KR (1) | KR100199510B1 (en) |
| CN (1) | CN1084643C (en) |
| DE (1) | DE69521968T2 (en) |
| TW (1) | TW284707B (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPP455098A0 (en) * | 1998-07-07 | 1998-07-30 | Commonwealth Scientific And Industrial Research Organisation | Process for chlorine recovery |
| BR0007634A (en) * | 1999-01-22 | 2001-12-18 | Sumitomo Chemical Co | Chlorine production process |
| BRPI0008181B8 (en) * | 2000-01-19 | 2017-03-21 | Sumitomo Chemical Co | Chlorine preparation process. |
| CN1911512B (en) * | 2005-07-07 | 2011-12-07 | 独立行政法人产业技术综合研究所 | Fluorination catalysts, method for their preparation, and method for producing fluorinated compounds using the catalysts |
| DE102006023261A1 (en) * | 2006-05-18 | 2007-11-22 | Bayer Materialscience Ag | Process for the production of chlorine from hydrogen chloride and oxygen |
| DE102006024548A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Materialscience Ag | Process for the oxidation of a hydrogen chloride-containing gas |
| DE102006024549A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Materialscience Ag | Process for the preparation of organic isocyanates |
| DE102006024542A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Materialscience Ag | Process for the separation of carbon monoxide from a hydrogen chloride-containing gas |
| DE102006024516A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Materialscience Ag | Process for the production of chlorine from hydrogen chloride and oxygen |
| DE102006024506A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Materialscience Ag | Process for the production of chlorine from hydrogen chloride and oxygen |
| DE102007020096A1 (en) | 2007-04-26 | 2008-10-30 | Bayer Materialscience Ag | Process for the oxidation of carbon monoxide in a gas stream containing HCl |
| DE102007020146A1 (en) | 2007-04-26 | 2008-10-30 | Bayer Materialscience Ag | Process for the purification and oxidation of a gas containing hydrogen chloride |
| DE102007020444A1 (en) | 2007-04-27 | 2008-11-06 | Bayer Materialscience Ag | Process for the oxidation of a hydrogen chloride-containing gas mixture |
| EP2198959A4 (en) * | 2007-09-27 | 2014-06-04 | Mitsui Chemicals Inc | Catalyst, method for producing the same, and method for producing chlorine using the catalyst |
| DE102008051694A1 (en) | 2008-10-15 | 2010-04-22 | Bayer Materialscience Ag | Process for the separation of carbon monoxide from a crude HCI gas |
| CN102341173B (en) * | 2009-03-26 | 2014-05-21 | 三井化学株式会社 | Catalyst for production of chlorine and process for production of chlorine using the catalyst |
| DE102009024525A1 (en) | 2009-06-06 | 2010-12-16 | Bayer Materialscience Ag | Process for the preparation of phosgene from carbon monoxide and hydrogen chloride |
| KR20120036956A (en) * | 2009-06-10 | 2012-04-18 | 바스프 에스이 | Method for hydrogen chloride oxidation at a catalyst having low surface roughness |
| SG174715A1 (en) | 2010-03-30 | 2011-10-28 | Bayer Materialscience Ag | Process for preparing diaryl carbonates and polycarbonates |
| CN102513093B (en) * | 2011-12-01 | 2013-06-12 | 连云港阳方催化科技有限公司 | High-concentration salt-containing wastewater liquid phase oxidation catalyst, preparation method thereof and treatment method |
| JP6788684B2 (en) * | 2016-12-02 | 2020-11-25 | 三井化学株式会社 | Chlorine production method by hydrogen chloride oxidation |
| CN106861714B (en) * | 2017-02-09 | 2019-08-27 | 西安近代化学研究所 | A kind of catalyst of hydrogen chloride conversion preparing chlorine gas |
| CN106861707B (en) * | 2017-02-09 | 2019-08-27 | 西安近代化学研究所 | A kind of preparation method of preparing chlorine by oxidizing hydrogen chloride catalyst |
| CN115845855A (en) * | 2022-12-09 | 2023-03-28 | 上海氯碱化工股份有限公司 | Hydrogen fluoride resistant catalyst for preparing chlorine by hydrogen chloride catalysis and preparation method thereof |
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- 1995-11-03 US US08/552,775 patent/US5707919A/en not_active Expired - Lifetime
- 1995-11-07 EP EP95307939A patent/EP0711599B1/en not_active Expired - Lifetime
- 1995-11-07 DE DE69521968T patent/DE69521968T2/en not_active Expired - Fee Related
- 1995-11-14 KR KR1019950041178A patent/KR100199510B1/en active IP Right Grant
- 1995-11-14 CN CN95118842A patent/CN1084643C/en not_active Expired - Lifetime
- 1995-11-17 TW TW084112200A patent/TW284707B/zh active
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| GB1461846A (en) * | 1973-03-22 | 1977-01-19 | Sumitomo Chemical Co | Process for producing highly chlorinated hydrocarbons |
| CN87105455A (en) * | 1986-06-26 | 1988-10-12 | 三井东圧化学株式会社 | The manufacture method of chlorine |
| CN88101489A (en) * | 1987-03-18 | 1988-10-05 | 三井东圧化学株式会社 | The manufacture method of chlorine |
| CN1036188A (en) * | 1988-03-01 | 1989-10-11 | 三井东圧化学株式会社 | A kind of method of producing chlorine |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69521968T2 (en) | 2001-11-15 |
| US5707919A (en) | 1998-01-13 |
| DE69521968D1 (en) | 2001-09-06 |
| KR100199510B1 (en) | 1999-06-15 |
| EP0711599A1 (en) | 1996-05-15 |
| EP0711599B1 (en) | 2001-08-01 |
| CN1126637A (en) | 1996-07-17 |
| TW284707B (en) | 1996-09-01 |
| KR960016957A (en) | 1996-06-17 |
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